CN106414801A

CN106414801A - Copper colloid catalyst solution for electroless copper plating and electroless copper plating method

Info

Publication number: CN106414801A
Application number: CN201680001548.5A
Authority: CN
Inventors: 内田卫; 田中薰; 田中雄也
Original assignee: Ishihara Chemical Co Ltd
Current assignee: Ishihara Chemical Co Ltd
Priority date: 2015-02-19
Filing date: 2016-01-14
Publication date: 2017-02-15
Anticipated expiration: 2036-01-14
Also published as: CN106414801B; WO2016132786A1; JP2016151056A; KR101831100B1; KR20170008289A; TW201631208A; TWI684673B; JP6209770B2

Abstract

The stability of a catalyst solution over time is notably improved by performing a preliminary adhesion-promoting treatment of soaking a non-electrically conductive substrate in a surfactant-containing solution and then applying a catalyst on the non-electrically conductive substrate with a copper colloid catalyst solution for electroless copper plating that contains (A) a soluble copper salt, (B) a reducing agent, (C) a colloid stabilizer, and (D) a specific sugar such as glucose, maltose, xylitol, sorbitol, etc. and performing electroless copper plating. Moreover, since the catalyst is applied and electroless plating is performed after catalyst activity has been increased by the preliminary adhesion-promoting treatment, the deposited copper film has an excellent appearance.

Description

Electroless copper copper colloid catalyst liquid and electroless copper plating method

Technical field

The present invention relates to when electroless copper is implemented to non-conductive substrate, for carrying out assigning as the catalyst of pretreatment The copper colloid catalyst liquid that gives, the electroless copper plating method using this catalyst liquid and the copper envelope that formed using the method Non-conductive substrate, provides the ageing stability that can significantly improve copper catalyst liquid, gives the technology of copper envelope excellent appearance Scheme.

Background technology

In order in the conductive board with copper or copper alloy substrate as representative, or with glass-epoxy resin, glass- The resin substrates such as polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, PET resin are generation Table, including enforcement electroless copper on the non-conductive substrate of glass substrate, ceramic substrate etc., the method generally adopting is：First Make the precious metal adsorption such as palladium, silver, platinum as catalyst core on substrate, then made using chemical bronze plating liquid by this catalyst core Copper envelope is separated out on substrate.

On the other hand, also do not use urging of noble metal catalyst using special metals such as cheap copper, nickel, cobalts Agent adding method, the general principle of the method is：In the catalyst liquid of this special metal, with reducing agent processing soluble gold Belong to salt, generate the colloidal particle of metal, and as catalyst core.

Wherein, the prior art of copper colloid catalyst liquid is listed below：Patent document 1 discloses that and adding soluble copper Salt, dispersant (gelatin, nonionic surface active agent), complexing agent (dicarboxylic acids, hydroxycarboxylic acid (oxycarboxylic acid) Deng), carry out after reduction treatment using reducing agent (sodium borohydride, dimethylamine borane (dimethylamine borane) etc.), then Add stabilizer (sodium hypophosphite, dimethylamine borane etc.) and make the fine copper catalyst liquid for electroless copper.

Patent document 2 discloses that and plated body is given by mantoquita (being copper-amine complex in preparation example 2), anionic surface Activating agent and reducing agent composition chemical plating catalyst, implement electroless copper after, then implement electro-coppering (claim 1～2, Paragraph 42).

Patent document 3 discloses that and using cupric oxide (I) colloidal catalytic agent solution, substrate is carried out after catalyst imparting, by base Plate impregnated in the solution containing mantoquita, reducing agent and complexing agent, direct copper plating on substrate.

Patent document 4 discloses that using containing surfactant (cationic, both sexes, nonionic etc., paragraph 56) Conditioning agent pre-processes to plated body, reuses containing cuprous salt, hypophosphites and chlorion or and then containing reduction The catalyst solution of agent (amine borine class, hydroboron class etc.) carries out the electroless copper plating method (claim 8 of catalyst treatment ～9, paragraph 70).

If patent document 4 has also stated that especially uses cationic surface active agent in above-mentioned conditioning agent, adsorb The hydrophilic group of the surfactant on plated body is negatively charged, and above-mentioned univalent copper ion becomes prone to adsorb (paragraph 58).

Patent document 5 describes using the activator containing noble metal/metal-colloid (colloidal solution of such as palladium/tin) Dispersion liquid non-conductive substrate is processed, then, with the conductive liquid solution containing copper salt solution, complexing agent and reducing agent After contact, carry out chemical plating and electric plating method (paragraph 1,13,24,29,65, table 1).

The general principle of above-mentioned water system catalyst liquid is to generate metal superfine grain using reducing agent processing soluble slaine Son, but actually including the catalyst liquid of above-mentioned patent document 1～5, the catalyst liquid of this principle generally mostly through when Stability aspect has problems, and is difficult the long-time continuity smoothly keeping catalyst imparting and plating operation.

If ageing stability reduces, implement electroless copper even if carrying out catalyst and giving, the feelings of envelope also occur Condition, or have that local does not separate out the plated film defect of envelope or plated film produces speckle, also or the problems such as lack of homogeneity.

For example, using build the bath initial stage catalyst liquid process after carry out chemical plating copper envelope when, build during bath through when steady Qualitative lower poorer by film outward appearance, but also need to consider to build the ageing stability of several months unit after bath.Even if that is, Using the catalyst liquid building the bath initial stage process by film outward appearance good in the case of, if bathed after the several months using self-built Catalyst liquid carries out processing, and is produced above-mentioned plated film defect by film outward appearance or the situation of speckle is quite a few, therefore the warp of catalyst liquid When stability critically important.

Therefore, the applicant proposes in Japanese Patent Application 2014-022271 (hereinafter referred to as first invention) and passes through Adding in copper catalyst liquid makes the stable hydroxycarboxylic acid of mantoquita, aminocarboxylic acids isocolloid stabilizer, adjusts mantoquita simultaneously With the blending ratio of this stabilizer, and make surfactant content be zero or by its content suppress below very small amount, from And improve the copper colloid catalyst liquid of the ageing stability of catalyst liquid.

If in view of chemical plating gained copper by the reduction of the raising of film outward appearance or processing cost, expecting to improve further and urge The ageing stability of agent liquid.

Therefore, it is conceived to whether adding carbohydrate in catalyst liquid can impact to the ageing stability of catalyst liquid, And extract and be included in the patent document carrying out the technology contents using carbohydrate during electroless copper after catalyst gives, then following institute Show.

(1) patent document 6

Metal salt back is carried out catalyst imparting process by non-conductive substrate, then the side carrying out electroless copper process Method (claim 1, paragraph 1), the composition carrying out above-mentioned catalyst imparting comprises glucose (glucose), galactolipin, malt The reduced sugar such as sugared (maltose), fructose (fructose), wood sugar (xylose) (claim 1,10, paragraph 1,24).In addition, The buffer such as citric acid, tartaric acid, malic acid (paragraph 19) also can be contained in above-mentioned composition.

Similar existing document includes Japanese Unexamined Patent Publication 2012-127002 publication (Rohm＆Haas).

(2) patent document 7

Slaine (mantoquita etc.) reduction is carried out catalyst imparting process by non-conductive substrate, then carries out chemical plating Copper treatment method (claim 1,3, paragraph 29, table 1), above-mentioned reducing agent can include glucose (paragraph 25).In addition, it is logical Cross and the carbohydrates such as the carboxylic acids such as tartaric acid, citric acid, butanedioic acid, sucrose, fructose are dissolved in catalyst solution, catalysis can be improved The adhesion amount (paragraph 31) to substrate surface for the agent metal.

(3) patent document 8

Carry out catalyst imparting process using elargol body catalyst liquid (pretreatment fluid) rather than copper catalyst liquid, then carry out The method (claim 1,35) of electroless copper.

In above-mentioned catalyst liquid, in addition to adding the hydroxycarboxylic acids such as citric acid, tartaric acid, lactic acid, malic acid, (right will Ask 1,3), the known colloidal dispersant such as cellulose and its derivates, monosaccharide, polysaccharide and its derivative can also be added (paragraph 46).

Monosaccharide, polysaccharide and its derivative are sucrose, mannitol, sorbierite, glycerine, dextrin etc. (paragraph 50).

(4) patent document 9

The non-conductive substrate that resin molded body is made is etched process so as to contact contains precious metal chemical complex (gold, silver etc.) and the colloidal solution of tin salt, the aqueous solution then contacting palladium compound carries out catalyst imparting process, then carries out The method (claim 1～2) that electroless copper is processed.

Glucose, sorbierite (sorbit), cellulose, sucrose, mannitol (mannite), glucolactone etc. have The carbohydrate of reproducibility can be added in chemical bronze plating liquid rather than above-mentioned catalyst liquid in (paragraph 73).

(5) patent document 10

The non-conductive substrates such as resin, pottery, glass carry out etch processes, make pink salt (stannous chloride etc.) adhere to into Row sensingization is processed, and impregnated in and displaces silver formation tin-silver composite in silver nitrate solution on tin, then it is molten to impregnated in reproducibility Activated in liquid, then carried out the method (claim 1～6, paragraph 10,22) of electroless copper, in above-mentioned reducing solution Glucose can be used.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication H02-093076 publication

Patent document 2：Japanese Unexamined Patent Publication H10-229280 publication

Patent document 3：Japanese Unexamined Patent Publication H07-197266 publication

Patent document 4：Japanese Unexamined Patent Publication 2011-225929 publication

Patent document 5：Japanese Unexamined Patent Publication 2013-522476 publication

Patent document 6：Japanese Unexamined Patent Publication 2012-130910 publication

Patent document 7：Japanese Unexamined Patent Publication 2003-313670 publication

Patent document 8：Japanese Unexamined Patent Publication 2004-190042 publication

Patent document 9：Japanese Unexamined Patent Publication 2006-299366 publication

Patent document 10：Japanese Unexamined Patent Publication 2005-146330 publication

Content of the invention

Problems to be solved by the invention

In above-mentioned patent document 6～10, the catalyst liquid as pretreating agent uses glucose, fructose, maltose, fiber The sugar alcohol such as the carbohydrates such as element or mannitol, sorbierite.

But, in patent document 9, carbohydrate, the sugar alcohol non-catalytic liquid for chemical bronze plating liquid.

The technical problem to be solved is, to its characteristic chemical constituent group on the basis of above-mentioned first invention One-tenth is extended, and improves the ageing stability of copper colloid catalyst liquid further.

The present inventor with above-mentioned patent document 6～10 as starting point, to being added with the carbohydrate comprising carbohydrate, sugar alcohol (carbohydrate) copper colloid catalyst liquid and the relation of its ageing stability have made intensive studies, if it is found that choosing Select specific carbohydrate to be added in copper colloid catalyst liquid, then can be effectively compared with the situation not having carbohydrate Improve the ageing stability of catalyst liquid, even if it has further been found that the carbohydrate beyond adding specific carbohydrate is above-mentioned Ageing stability also will not improve or can reduce on the contrary, thus completing the present invention.

Method for solve problem

That is, the present invention 1 is a kind of electroless copper copper colloid catalyst liquid, and it is for leading with enforcement the non-of electroless copper Electrical substrate contact carries out the copper colloid catalyst liquid of catalyst imparting, contains：

(A) soluble copper salt；

(B) reducing agent；

(C) it is selected from the deflocculant in monocarboxylic acid class, hydroxycarboxylic acid, aminocarboxylic acids and polybasic carboxylic acid class At least one；And

(D) be selected from glucose, fructose, lactose, maltol, isomaltoketose (isomaltulose), wood sugar, sorbierite, Xylitol, mannitol, maltitol, antierythrite, reduction starch syrup (reduced starch syrup), lactitol, also The former at least one sending the carbohydrate in Latin sugar and glucolactone.

The present invention 2 is, in the invention described above 1, soluble-salt (A) is A with the content mol ratio of deflocculant (C):C =1:0.03～1:35 electroless copper copper colloid catalyst liquid.

The present invention 3 is, in the invention described above 1 or 2, contains further selected from polyethylene glycol, polypropylene glycol, polyethylene pyrrole At least one change of the synthesis class water-soluble polymer in pyrrolidone, polyvinyl alcohol, polyacrylamide and polyethyleneimine Learn copper facing copper colloid catalyst liquid.

The present invention 4 is, in any one of the invention described above 1～3, reducing agent (B) is selected from hydroboron, amine borine Class, hypophosphorous acid class, aldehydes, Vitamin C acids, hydrazine, polyatomic phenol, polynary aphthols, phenolsulfonic acid class, naphtholsulfonic acid class, with And the copper colloid catalyst liquid of at least one electroless copper in sulfinic acid class.

The present invention 5 is, in any one of the invention described above 1～4, the monocarboxylic acid class in deflocculant (C) is choosing From formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid and At least one in their salt；

Hydroxycarboxylic acid be selected from citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic, lactic acid, three Hydroxybutyric acid (trioxybutyric acid), ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, bright At least one in propylhomoserin, citramalic acid and their salt；

Aminocarboxylic acids is selected from hydroxyethylethylene diamine tri-acetic acid, diethylene-triamine pentaacetic acid, trien six Acetic acid, ethylenediamine tetra-acetic acid, ethylenediamine tetrapropionic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, imido Base dipropionic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid (1,3-propanediamine tetraacetic acid), 1,3- diaminourea -2- Hydroxy propane tetraacethyl (1,3-diamino-2-hydroxypropane tetraacetic acid), glycol ether diamines four Acetic acid, m-phenylene diamine (MPD) tetraacethyl, 1,2- cyclohexanediamine-N, N, N ', N '-tetraacethyl, diaminopropionic acid, glutamic acid, two carboxymethyls Glutamic acid (dicarboxy methyl glutamate), ornithine, cysteine, N, N- bis- (2- ethoxy) glutamic acid, (S, S at least one in)-ethylenediamine butanedioic acid and their salt；

Polybasic carboxylic acid class (C) be selected from butanedioic acid, glutaric acid, malonic acid, adipic acid, ethanedioic acid, maleic acid, citraconic acid, At least one electroless copper in itaconic acid, mesaconic acid and their salt copper colloid catalyst liquid.

The present invention 6 is a kind of electroless copper plating method, and it includes：

A () absorption promotes operation (pretreatment process), non-conductive substrate is immersed in the liquid containing adsorption enhancer In, this adsorption enhancer be selected from nonionic surface active agent, cationic surface active agent, anionic surfactant, And at least one in amphoteric surfactant；

B () catalyst gives operation, non-conductive substrate is immersed in the copper colloid of any one of the invention described above 1～5 In catalyst liquid, make copper colloid particle absorption on the surface of the substrate；And

C () Electroless Plating Procedure, forms copper envelope using chemical bronze plating liquid on the aforesaid substrate through adsorption treatment.

The present invention 7 is, in the invention described above 6, the adsorption enhancer of operation (a) be cationic surface active agent and/ Or the electroless copper plating method of amphoteric surfactant.

The present invention 8 is to form the non-conductive substrate of copper envelope using the electroless copper plating method of the invention described above 6 or 7.

The effect of invention

It is proposed that being immersed in non-conductive substrate containing mantoquita, reducing agent and colloid-stabilised in above-mentioned first invention In the copper catalyst liquid of agent, thus separating out the good copper quilt of outward appearance in next step electroless copper operation using its catalyst activity Film.

In the present invention, by increasing particular carbon water further in the essential component of the copper catalyst liquid of this first invention Compound, can significantly improve the ageing stability of catalyst liquid, obtain the copper envelope of excellent appearance by chemical plating.

Even if also very stable through several months colloid catalyst liquid especially from building bath, therefore, it is possible to obtain excellent appearance Envelope, and the maintenance of catalyst liquid can be mitigated, improve the productivity ratio of electroless copper.

As the pretreatment of electroless copper, there is the catalyst carrying out using tin-palladium etc. to give in the past, and in the present invention not Using noble metal, therefore can reduce the cost of substrate manufacture, remove without the palladium that substrate will be given.

In addition, if carried out absorption using surfactant before catalyst imparting is carried out to non-conductive substrate promoting Process, then can improve the effect of copper colloid catalyst.If especially processed with cationic surface active agent, copper The effect is significant of colloid catalyst improves.

Specific embodiment

A first aspect of the present invention is electroless copper copper colloid catalyst liquid, and it is for contacting with non-conductive substrate Carry out the copper colloid catalyst liquid of catalyst imparting, containing (A) soluble copper salt, (B) reducing agent and (C) deflocculant, and And also contain (D) specific carbohydrate；Second aspect is the electroless copper plating method of the catalyst liquid using above-mentioned first aspect, The method is carried out to non-conductive substrate with the liquid containing surfactant adsorbing promotion process, then, using above-mentioned in advance Catalyst liquid carries out electroless copper after carrying out catalyst imparting；The third aspect is to be formed using the electroless copper plating method of second aspect The non-conductive substrate of copper envelope.

Above-mentioned non-conductive substrate refers to, with glass-epoxy resin, glass-polyimide resin, epoxy resin, polyamides The resin substrates such as imide resin, polycarbonate resin, ABS resin, PET resin represent, including glass substrate, ceramic substrate etc..

The essential component of the copper colloid catalyst liquid of the invention described above 1 is (A) soluble copper salt, (B) reducing agent, (C) glue Body stabilizer and (D) specific carbohydrate.

Above-mentioned soluble-salt (A) is as long as the soluble-salt producing monovalence or bivalent cupric ion in aqueous then can make Use any soluble-salt, be not particularly limited, be also not excluded for indissoluble salt.Specifically, can include copper sulphate, cupric oxide, Copper chloride, cupric pyrophosphate, copper carbonate；Or the carboxylic acid mantoquitas such as copper acetate, ethanedioic acid copper and copper citrate；Also or copper methane sulfonate and Organic sulfonic acid mantoquita such as ethylenehydrinsulfonic acid copper etc., preferably copper sulphate, copper citrate, copper methane sulfonate.

As above-mentioned reducing agent (B), hydroboron, amine borine class, hypophosphorous acid class, aldehydes, ascorbic acid can be included Class, hydrazine, polyatomic phenol, polynary aphthols, phenolsulfonic acid class, naphtholsulfonic acid class, sulfinic acid class etc..Aldehydes is formaldehyde, acetaldehyde Acid or its salt etc., polyatomic phenol is catechol, hydroquinones, resorcinol, pyrogallol, phloroglucin, gallic acid etc., Phenolsulfonic acid class is phenolsulfonic acid, cresol sulfonic acid or its salt etc..

Above-mentioned deflocculant (C) is to form copper complex formazan compound in plating bath, plays the warp ensureing catalyst liquid When stability function.

This deflocculant (C) is selected from monocarboxylic acid class, hydroxycarboxylic acid, aminocarboxylic acids and polybasic carboxylic acid class.

As above-mentioned monocarboxylic acid class, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, capric acid, the moon can be included Cinnamic acid, myristic acid, palmitic acid, stearic acid and their salt etc..

As above-mentioned hydroxycarboxylic acid, citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, second can be included Alkyd, lactic acid, trihydroxy-butyric acid, ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine, lemon apple Acid and their salt etc..

As above-mentioned aminocarboxylic acids, ethylenediamine tetra-acetic acid (EDTA), hydroxyethylethylene diamine tri-acetic acid can be included (HEDTA), diethylene-triamine pentaacetic acid (DTPA), triethylenetetraaminehexaacetic acid (TTHA), ethylenediamine tetrapropionic acid, ammonia three second Sour (NTA), iminodiacetic acid (IDA), dipropionic acid (IDP), hydroxyethyliminodiacetic acid, 1,3- propane diamine tetrem Acid, 1,3- diaminourea -2- hydroxy propane tetraacethyl, glycoletherdiaminotetraacetic acid, m-phenylene diamine (MPD) tetraacethyl, 1,2- hexamethylene two Amine-N, N, N ', N '-tetraacethyl, diaminopropionic acid, glutamic acid, two carboxymethyl glutamic acid, ornithine, cysteine, N, N- bis- (2- ethoxy) glutamic acid, (S, S)-ethylenediamine butanedioic acid and their salt etc..

As above-mentioned polybasic carboxylic acid class, can include butanedioic acid, glutaric acid, malonic acid, adipic acid, ethanedioic acid, maleic acid, Citraconic acid, itaconic acid, mesaconic acid and their salt etc..

The colloid catalyst liquid of the present invention has the feature selecting to add specific carbohydrate (D).

Above-mentioned carbohydrate (D), primarily to improving the ageing stability of colloid catalyst liquid and adding, is selected from Glucose (glucose), fructose (fructose), lactose (lactose), maltose (maltose), isomaltoketose (draw by group Tetrose), wood sugar, sorbierite, xylitol, mannitol, maltitol, antierythrite, reduction starch syrup, lactitol, reduction different Maltulose, glucolactone.

Above-mentioned glucose, fructose, wood sugar etc. belong to monosaccharide, and glucolactone belongs to the derivative of monosaccharide, lactose, Maltose etc. belongs to disaccharides, and sorbierite, xylitol, mannitol etc. belong to sugar alcohol, and the concept of the carbohydrate of the present invention Including above-mentioned glucide and its ramification, sugar alcohol.

Above-mentioned reduction starch syrup refers to that the aldehyde radical of the specific above-mentioned carbohydrate such as glucose, maltose is reduced into hydroxyl Starch syrup.In addition, as above-mentioned carbohydrate (D), the specific monosaccharide such as glucose, fructose, wood sugar is by more than 3 sugar The oligomer that glycosidic bond is polymerized is similarly effective.

On the other hand, above-mentioned carbohydrate selects from special component, thus be excluded that starch, dextrin etc..

Preferably carbohydrate can include glucose, fructose, lactose, maltose, sorbierite, xylitol, mannitol, Glucolactone, substantially preferred sugar alcohol.

The copper colloid catalyst liquid of the present invention is water system, and therefore liquid flux is defined to water and/or hydrophily alcohol, and exclusion has Machine solvent (including lipophile alcohol) is used alone.

In addition, with regard to this catalyst liquid, due to being easily reduced near neutral catalyst activity, therefore preferred catalyst liquid PH value in the acidic side in addition to neutral region or alkaline side, specifically pH1～6 and 8～12 more suitable, preferably PH2～5 and 8～11, if pH value is adjusted to pH2～5 and 8～11, copper colloidal particle is easy to stabilize.

In copper colloid catalyst liquid, above-mentioned soluble copper salt (A) can be used alone or is used in combination, and its content is 0.005～3 Mole/L, preferably 0.05～2 mole/L, more preferably 0.04～1.2 mole/L.

Above-mentioned reducing agent (B) can be used alone or is used in combination, and its content is 0.005～4 mole/L, and preferably 0.02～3 Mole/L, more preferably 0.03～2.2 mole/L.If the content of reducing agent is less than appropriate amount, the reduction of mantoquita reduces, If otherwise the homogenieity crossing the copper envelope that at most chemical plating is separated out may reduce.

Above-mentioned deflocculant (C) can be used alone or is used in combination, and its content is 0.005～4 mole/L, and preferably 0.01 ～2 moles/L, more preferably 0.05～1.6 mole/L.

Above-mentioned carbohydrate (D) can be used alone or is used in combination, and its content is 0.001～4 mole/L, and preferably 0.01 ～3 moles/L, more preferably 0.05～2.2 mole/L.

In copper colloid catalyst liquid, above-mentioned (A) is A with the content mol ratio of (C):C=1:0.03～1:35, preferably A:C=1:0.5～1:24.If the relative amount of deflocculant (C) is very few, the ageing stability of catalyst liquid reduces, And then also become the bad main cause of chemical plating gained copper envelope generation precipitation.Whereas if the content of deflocculant (C) Excessively, then can damage the ageing stability of catalyst liquid, make the Quality Down (with reference to aftermentioned test example) of gained copper envelope.

In copper colloid catalyst liquid, above-mentioned (A) is A with the content mol ratio of (B):B=1:0.01～1:6, preferably A:B=1:0.05～1:4, more preferably A:B=1:0.07～1:2.

In copper colloid catalyst liquid, above-mentioned (A) is A with the content mol ratio of (D):D=1:0.01～1:40, preferably A:D=1:0.1～1:25, more preferably A:D=1:1～1:15.If the relative amount of carbohydrate (D) is excessive, instead And colloid catalyst liquid excessively stabilisation can be made to lose catalyst activity it is possible to assign to the catalyst core of non-conductive substrate Give, and then the envelope good to outward appearance forms and cause obstacle.

When preparing this catalyst liquid, due to smoothly supplying electron from reducing agent to copper ion, it is substantially therefore The consuming time lentamente instills reductant solution in the solution containing soluble copper salt (and deflocculant) and is prepared. For example, (excellent by the reductant solution instillation copper salt solution of 5～50 DEG C (preferably 10～40 DEG C), stirring 20～1200 minutes Elect 30～300 minutes as), make catalyst liquid.Should illustrate, in the preparation of catalyst liquid, also be not excluded for soluble copper Salting liquid instills in reductant solution.

In the catalyst liquid of the present invention, the copper colloidal particle being generated by soluble copper salt by the effect of reducing agent is suitable Preferably average grain diameter is 1～250nm, the minuteness particle of preferably 1～120nm, more preferably 1～100nm.

If the average grain diameter of copper colloidal particle is below 250nm, may infer that to be immersed in non-conductive substrate and urge When in agent liquid, colloidal particle enters the recess in the micro concavo-convex face of substrate, by densely adsorbing or tangling etc. anchoring effect, Promote to give copper colloid core to substrate surface.Whereas if average grain diameter is more than 250nm, then not only because of cohesion, precipitation or can divide It is difficult to obtain stable copper colloid from grade, and anchoring effect is also undesirable, therefore can only give copper to substrate surface local Colloidal particle, or it is bad to be possible to appearance imparting.

Surfactant can be contained in the copper colloid catalyst liquid of the present invention 1, but because catalyst activity is likely to decrease, The content of therefore preferred surfactant suppresses in below 950mg/L.

Above-mentioned surfactant refers to the various surfactants of nonionic, both sexes, cationic or anionic, Especially not preferred both sexes, cationic, anionic or low molecular nonionic surface active agent.

As above-mentioned nonionic surface active agent, can include：C1～C20 fatty alcohol, phenol, naphthols, bisphenols, (gathering) C1～C25 alkyl phenol, (gathering) aryl alkyl phenol, C1～C25 alkyl naphthol, C1～C25 alkoxylated phosphate (salt), dehydration 2～300 moles of epoxies of addition condensation in sorbitol ester, PAG, C1～C22 fatty amine, C1～C22 fatty acid amide etc. The compound of ethane (EO) and/or expoxy propane (PO) or C1～C25 alkoxylated phosphate (salt) etc..

As above-mentioned cationic surface active agent, quaternary ammonium salt or pyridiniujm etc. can be included, specifically can include： Dodecyl trimethyl ammonium salt, octadecyltrimethylammonium salt, dodecyl dimethyl ethyl ammonium salt, octadecyldimethyl second Base ammonium salt, dimethyl benzyl dodecyl ammonium salt, cetyldimethylbenzylammonium salt, octadecyl dimethyl benzyl ammonium salt, Trimethyl benzyl ammonium salt, triethylbenzyl ammonium salt, dimethyl diphenyl ammonium salt, benzyl dimethyl phenyl ammonium salt, cetyl pyrrole Pyridine salt, dococylpyridinium salt, dococylpyridinium salt, stearyl amine acetate, bay amine acetate, octadecylamine acetate Deng.

As above-mentioned anionic surfactant, alkyl sulfate, polyoxyethylene alkyl ether sulfate salt can be included, gather Oxygen vinyl alkyl phenyl ether sulfate, alkylbenzenesulfonate, [(mono-, di-, three) alkyl] naphthalene sulfonate etc..

As above-mentioned amphoteric surfactant, carboxybetaine, imidazolinium betaine, sulfobetaines, ammonia can be included Yl carboxylic acid etc..Furthermore it is also possible to the sulfuric acid of the condensation product using oxirane and/or expoxy propane and alkylamine or diamines Change or sulfonated adduct.

In order to improve the dispersiveness of colloidal particle, during electroless copper, obtain uniform and no speckle envelope, the copper of the present invention Synthesis class water-soluble polymer can be contained in colloid catalyst liquid.

If containing this synthesis class water-soluble polymer in catalyst liquid, the dispersiveness raising of colloidal particle, thus exist During electroless copper, contribute to separating out the copper envelope of excellent in uniformity and no speckle.

Above-mentioned synthesis class water-soluble polymer refers to exclude the water-soluble polymer of the natural origins such as gelatin, starch, and not Exclude the cellulose derivatives such as carboxymethylcellulose calcium (CMC), the methylcellulose (MC) of semi-synthetic class.

The catalyst liquid of the present invention 3 synthesize class water-soluble polymer containing object, with above-mentioned surfactant In relation, belong to composition therein and might have part repetition, but the two is different concepts in the present invention.

In the catalyst liquid of the present invention 3, it is not necessary condition containing the composition beyond water-soluble polymer, therefore for example Regardless of whether containing surfactant, that is, contain or not contain surfactant.

As shown in the present invention 3, as above-mentioned synthesis class water-soluble polymer, can include polyethylene glycol (PEG), poly- the third two Alcohol (PPG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyethyleneimine (PEI), poly- Acrylates etc., PEG, PVP, PVA of particularly preferred HMW etc..

Synthesis class water-soluble polymer can be used alone or be used in combination, its with respect to catalyst liquid content be 0.05～ 100g/L, preferably 0.5～50g/L, more preferably 1.0～30g/L.

The present invention 6 is the chemical plating method using above-mentioned copper colloid catalyst liquid, combined successively by three below operation and Become.

A () absorption promotes operation

B () catalyst gives operation

(c) electroless copper operation

Above-mentioned absorption promotes operation (a) to can be considered pretreatment (preliminary treatment) operation that the catalyst of operation (b) gives, and is Non-conductive substrate is immersed in the operation in the liquid containing adsorption enhancer, above-mentioned adsorption enhancer is selected from nonionic table In face activating agent, cationic surface active agent, anionic surfactant and amphoteric surfactant at least one Kind.Contacted with the liquid containing surfactant by making substrate, the wettability of substrate surface can be improved, strengthen catalyst and live Property, and promote the absorption of copper colloidal particle in subsequent processing.

Promote, in operation, to need to make non-conductive substrate contact with the liquid containing surfactant, therefore base in absorption It is to impregnate in a liquid but it is also possible to be coated on the liquid spray containing surfactant on substrate or with bristle in basis Substrate is first-class.

As shown in the present invention 7, from the viewpoint of promoting absorption, positively charged cationic or amphoteric surfactant More suitable, especially more preferably cationic surface active agent.In addition, if in cationic surface active agent and with a small quantity Nonionic surface active agent, then adsorbing facilitation effect increases further.

In the catalyst liquid of the present invention, reducing agent acts on the zeta electricity of the copper colloidal particle that soluble copper salt is generated Position is negative value, if therefore for example carrying out contact process with cationic surface active agent to non-conductive substrate, substrate is easy Positively charged, in subsequent processing, copper colloidal particle increases to the adsorption efficiency of substrate.

The concrete example of surfactant, as excluded in the catalyst liquid as the invention described above 1 or suppressing described by object The explanation of surfactant described in.

The content of surfactant is 0.05～100g/L, preferably 0.5～50g/L.Preferably comprise surfactant The temperature of liquid is 15～70 DEG C about, and dip time is 0.5～20 minute about.

After the non-conductive substrate pure water that absorption promotion process terminates, dry or moist, enter next step and urge Agent gives operation (b).

Give in operation in catalyst, non-conductive substrate is immersed in above-mentioned copper colloid catalyst liquid, makes copper colloid Particle absorption is on the surface of the substrate.

The liquid temperature of this catalyst liquid is 5～70 DEG C, is preferably 15～60 DEG C, and dip time is 0.1～20 minute, is preferably 0.2～10 minute, when carrying out impregnation process, in the state of substrate is statically placed in catalyst liquid dipping can but it is also possible to It is stirred or dynamic.

In addition, if inserting at pickling before this catalyst gives next step electroless copper operation (c) after operation (b) Science and engineering sequence, then compared with the situation not carrying out pickling, can promote the activity of this catalyst activity, further even if logical to having The substrate of the complicated shape of hole or through hole also can be reliably prevented the baneful influence that copper facing is uneven or breaks, and carries further The adaptation of high-copper envelope.

When carrying out pickling processes, the concentration of acid is 10～200g/L, is preferably 20～100g/L, and acid can use sulfuric acid, salt The organic acids such as the carboxylic acids such as the inorganic acids such as acid, organic sulfonic acid, acetic acid, tartaric acid, citric acid.

The treatment temperature of pickling is 5～70 DEG C, is preferably 15～60 DEG C, and process time is 0.1～20 minute, is preferably 0.2～10 minute.

After impregnated in the non-conductive substrate pure water in catalyst liquid, dry or moist, enter electroless copper Operation (c).

Electroless copper and prior art equally carry out processing, and are not particularly limited.The liquid temperature of chemical bronze plating liquid is usual For 15～70 DEG C, preferably 20～60 DEG C.

The stirring of copper plating bath can adopt mechanical agitation of air stirring, the stirring of quick liquor stream, stirring vane etc. etc..

The present invention 8 is to form the non-conductive substrate of copper envelope using above-mentioned electroless copper plating method, refers to via the present invention 6 Absorption promote, catalyst give, chemical plating and form the aforesaid substrate of copper envelope.

Non-conductive substrate is as described above, referring to glass-epoxy resin, glass-polyimide resin, epoxy resin, gathering The resin substrates such as imide resin, or glass substrate, ceramic substrate etc..

The composition of chemical bronze plating liquid is not particularly limited, it is possible to use known copper plating bath.

Chemical bronze plating liquid substantially contains soluble copper salt, reducing agent and complexing agent, or can also contain table further The various additives such as face activating agent or pH adjusting agent or acid.

With regard to soluble copper salt, as shown in the above-mentioned description to copper colloid catalyst liquid.

With regard to contained reducing agent in chemical bronze plating liquid, also described above to shown in the description of copper colloid catalyst liquid, with first Aldehyde (formalin) is representative, including hypophosphorous acid class, phosphorous acids, amine borine class, boron hydrogen species, glyoxalic acid etc., preferably formalin.

With regard to contained complexing agent in chemical bronze plating liquid, also include steady with the colloid described in above-mentioned copper colloid catalyst liquid Determine the general part of agent, specifically：Ethylenediamine tetra-acetic acid (EDTA), diethylene-triamine pentaacetic acid (DTPA), Sanya second Urotropine six acetic acid (TTHA), hydroxyethylethylene diamine tri-acetic acid (HEDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA) Deng aminocarboxylic acids；Ethylenediamine, tetra-methylenedimine, hexamethylene diamine, diethylenetriamines, tetren, five Asias Many amines such as hexamine；The alkamines such as MEA, diethanol amine, triethanolamine；Citric acid, tartaric acid, lactic acid, apple The hydroxycarboxylic acids such as acid；TGA, glutamic acid etc..

In chemical bronze plating liquid, can containing organic acid and inorganic acid or its salt as liquid basic ingredient.

Above-mentioned inorganic acid can include sulfuric acid, pyrophosphoric acid, fluoboric acid etc..In addition, organic acid can include glycolic or wine Organic sulfonic acids such as the hydroxycarboxylic acids such as stone acid, methanesulfonic acid or 2- ethylenehydrinsulfonic acid etc..

[embodiment]

Hereinafter, to the liquid containing adsorption enhancer, copper colloid catalyst liquid and the chemical bronze plating liquid including the present invention Preparation illustrate in the embodiment of interior electroless copper plating method, and the ageing stability to copper colloid catalyst liquid successively Illustrate with the evaluation test example of the outward appearance of gained copper envelope in above-described embodiment.

Should illustrate, the present invention is not limited to the following example, test example it is of course possible to technology design in the present invention In the range of carry out random variation.

《The embodiment of electroless copper plating method》

In the following example 1～20, embodiment 9～10 is the example containing synthesis class water-soluble polymer in catalyst liquid, In addition embodiment is the example without this water-soluble polymer, and embodiment 2～20 is about with embodiment 1 or embodiment 4 Based on, change over the example graded.

Embodiment 1 is citric acid to be used as deflocculant in catalyst liquid, xylitol (sugar alcohol) is used as carbon Hydrate, is used sodium borohydride and hypophosphorous acid as the example of reducing agent.Embodiment 2 is based on embodiment 1, by xylitol Content be adjusted to above-mentioned usual scope lower limit example, embodiment 3 is that the content of xylitol is adjusted to above-mentioned usual scope The upper limit example.Embodiment 4 is the example that carbohydrate uses sorbierite (sugar alcohol), and similarly embodiment 5 is carbohydrate Using the example of mannitol (sugar alcohol), embodiment 6 is the example that carbohydrate uses glucolactone (derivative of monosaccharide), Embodiment 7 is the example that carbohydrate uses glucose (monosaccharide), and embodiment 8 is that carbohydrate uses maltose (disaccharides Class) example.Embodiment 9 is that carbohydrate uses xylitol, synthesis class water-soluble polymer use polyvinylpyrrolidone it Example.Embodiment 10 is that carbohydrate uses sorbierite, and synthesis class water-soluble polymer uses the example of polyethylene glycol.Embodiment 11 It is carbohydrate the example (sugar alcohol simultaneously use-case to each other) with xylitol and sorbierite, similarly embodiment 12 is carbon aquation Compound the example (the simultaneously use-case of sugar alcohol and monosaccharide) with sweet dew alcohol and glucose.Embodiment 13 is to be changed based on embodiment 1 Become the example of soluble copper salt, embodiment 14 is the example changing soluble copper salt based on embodiment 4.Embodiment 15～16 be with Change the example of deflocculant, embodiment 17 is the example changing deflocculant based on embodiment 4 based on embodiment 1. Embodiment 18 be based on embodiment 4 change reducing agent example, embodiment 19 be based on embodiment 5 change reducing agent it Example.Embodiment 20 is the example being changed the pH value of catalyst liquid based on embodiment 1 to alkalescent area.

In addition, embodiment 4 and embodiment 11 are to insert pickling before catalyst gives electroless copper operation after operation The example of operation, other embodiment does not all carry out pickling, carries out successively adsorbing promotion → catalyst imparting → electroless copper each operation Example.

On the other hand, in following comparative example 1～3, comparative example 1 is not contain deflocculant and carbon aquation in catalyst liquid The blank example of compound both compositions.Comparative example 2 is to contain deflocculant in catalyst liquid, and contains and defined of the present invention The different carbohydrate (starch) of carbohydrate example.Comparative example 3 is that no absorption promotes operation, directly assigns from catalyst Operation is given to carry out the blank example of Electroless Plating Procedure.

In addition, benchmark example is carried out according to above-mentioned first invention, be therefore in catalyst liquid contain deflocculant but not Example containing carbohydrate given to this invention.

(1) embodiment 1

《Absorption promotes, catalyst gives and the process step of chemical plating》

First, non-conductive substrate is double-sided copper-clad glass-epoxy resin substrate (Matsushita Electric Industrial Co., Ltd FR- 4th, thickness of slab：1.0mm) as sample substrate.

Then, sample substrate is carried out, after absorption promotion, be immersed in aftermentioned (b) using the adsorption enhancer of aftermentioned (a) Carry out catalyst imparting, the plating solution reusing aftermentioned (c) carries out electroless copper in catalyst liquid.

Specifically, said sample substrate be impregnated under conditions of 50 DEG C, 2 minutes above-mentioned containing adsorption enhancer In liquid, then use pure water.Then, process the sample substrate after (pretreatment) at 25 DEG C, 10 points by implementing absorption promotion Impregnated under conditions of clock in above-mentioned copper colloid catalyst liquid, use pure water.Then, the sample after catalyst gives will be implemented Substrate impregnated in above-mentioned chemical bronze plating liquid, implements chemical plating under conditions of 50 DEG C, 10 minutes, forms copper on sample substrate After envelope, with pure water, the universe is dry.

(a) preparation containing the liquid of adsorption enhancer

It is prepared in accordance with the following composition the liquid containing adsorption enhancer.

[liquid containing adsorption enhancer]

The quaternary ammonium salt of diallylamine polymers：5g/L

Polyethylene oxide side chains decyl ethers：1g/L

PH value：10.0

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Xylitol：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 45 minutes in the above-mentioned copper solution of be adjusted to pH4.0 25 DEG C, make copper colloid Catalyst liquid.

The mol ratio of each composition of above-mentioned catalyst liquid is as follows.

Mantoquita:Deflocculant=1:2, mantoquita:Carbohydrate=1:3, mantoquita:Reducing agent=1:2

The average grain diameter of the copper colloidal particle generating is about 15nm.

The preparation of (c) chemical bronze plating liquid

Make electroless copper bath of liquid (building bath) according to following composition.This plating solution adjusts pH value with aftermentioned NaOH.

[chemical bronze plating liquid]

Copper sulfate pentahydrate is (with Cu²⁺Meter)：2.0g/L

Formaldehyde：5.0g/L

EDTA：30.0g/L

NaOH：9.6g/L

Surplus：Pure water

PH value (20 DEG C)：12.8

(2) embodiment 2

Based on above-described embodiment 1, it is prepared in accordance with the following composition copper colloid catalyst liquid, in addition, containing absorption The liquid of accelerator, the composition of chemical bronze plating liquid and absorption promote, catalyst gives, place's manage bar of electroless copper each operation Part is same as Example 1.

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Xylitol：0.001 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Mantoquita:Deflocculant=1:2, mantoquita:Carbohydrate=1:0.01, mantoquita:Reducing agent=1:2

The average grain diameter of the copper colloidal particle generating is about 25nm.

(3) embodiment 3

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Xylitol：4.0 moles/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Mantoquita:Deflocculant=1:2, mantoquita:Carbohydrate=1:40, mantoquita:Reducing agent=1:2

The average grain diameter of the copper colloidal particle generating is about 10nm.

(4) embodiment 4

Carry out successively adsorbing promotion, catalyst imparting, pickling, the example of electroless copper each operation.

Should illustrate, absorption promotion, catalyst imparting, the treatment conditions of electroless copper each operation and chemical bronze plating liquid Composition is same as Example 1, and each preparation condition of the liquid containing adsorption enhancer and copper colloid catalyst liquid is as follows.

In addition, the treatment conditions of pickling are as be described hereinafter shown in (d).

(a) preparation containing the liquid of adsorption enhancer

Prepare the liquid containing adsorption enhancer according to consisting of.

[liquid containing adsorption enhancer]

Dodecyl dimethyl benzyl ammonium chloride：5g/L

Polyethylene oxide side chains decyl ethers：1g/L

PH value：9.0

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Sorbierite：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

The average grain diameter of the copper colloidal particle generating is about 40nm.

The treatment conditions of (d) pickling

Prepare the sulfuric acid scrubbing liquid of 50g/L, by the sample substrate after processing through above-mentioned catalyst imparting at 45 DEG C, 1 minute Under conditions of impregnated in this cleaning solution, after washing, supply next step electroless copper operation.

(5) embodiment 5

Absorption promotion, the composition of catalyst imparting, the treatment conditions of electroless copper each operation and chemical bronze plating liquid and reality Apply that example 1 is identical, each preparation condition of the liquid containing adsorption enhancer and copper colloid catalyst liquid is as follows.

(a) preparation containing the liquid of adsorption enhancer

Prepare the liquid containing adsorption enhancer according to consisting of.

[liquid containing adsorption enhancer]

Dodecyl dimethyl oxyneurine：5g/L

NONIN HS 240：1g/L

PH value：10.5

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Mannitol：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

(6) embodiment 6

Absorption promotion, catalyst imparting, the treatment conditions of electroless copper each operation and the liquid containing adsorption enhancer Same as Example 1 with the composition of chemical bronze plating liquid, the preparation condition of copper colloid catalyst liquid is as follows.

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Glucolactone：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

The average grain diameter of the copper colloidal particle generating is about 20nm.

(7) embodiment 7

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Glucose：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

(8) embodiment 8

(a) preparation containing the liquid of adsorption enhancer

Prepare the liquid containing adsorption enhancer according to consisting of.

[liquid containing adsorption enhancer]

Dodecyl dimethyl benzyl ammonium chloride：5g/L

NONIN HS 240：1g/L

PH value：10.5

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Maltose：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 60 minutes in the above-mentioned copper solution of be adjusted to pH4.0 25 DEG C, make copper colloid Catalyst liquid.

(9) embodiment 9

(a) preparation containing the liquid of adsorption enhancer

Prepare the liquid containing adsorption enhancer according to consisting of.

[liquid containing adsorption enhancer]

Dodecyl dimethyl oxyneurine：5g/L

NONIN HS 240：1g/L

PH value：10.0

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Xylitol：0.3 mole/L

Polyvinylpyrrolidone (mean molecule quantity 40000)：2.0g/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 45 minutes in the above-mentioned copper solution of be adjusted to pH3.0 25 DEG C, make copper colloid Catalyst liquid.

(10) embodiment 10

(a) preparation containing the liquid of adsorption enhancer

Prepare the liquid containing adsorption enhancer according to consisting of.

[liquid containing adsorption enhancer]

Dodecyl dimethyl benzyl ammonium chloride：5g/L

Polyethylene oxide side chains decyl ethers：1g/L

PH value：10.0

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Sorbierite：0.3 mole/L

Polyethylene glycol (mean molecule quantity 10000)：1.0g/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 90 minutes in the above-mentioned copper solution of be adjusted to pH4.0 25 DEG C, make copper colloid Catalyst liquid.

The average grain diameter of the copper colloidal particle generating is about 35nm.

(11) embodiment 11

But, adsorb promotion, catalyst imparting, the treatment conditions of electroless copper each operation and contain adsorption enhancer Liquid and chemical bronze plating liquid composition same as Example 1, the preparation condition of copper colloid catalyst liquid is as follows.

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Sorbierite：0.2 mole/L

Xylitol：0.1 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 45 minutes in the above-mentioned copper solution of be adjusted to pH4.0 35 DEG C, make copper colloid Catalyst liquid.

The treatment conditions of (d) pickling

(12) embodiment 12

(a) preparation containing the liquid of adsorption enhancer

Prepare the liquid containing adsorption enhancer according to consisting of.

[liquid containing adsorption enhancer]

Dodecyl dimethyl benzyl ammonium chloride：5g/L

Polyethylene oxide side chains decyl ethers：1g/L

PH value：8.5

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Mannitol：0.2 mole/L

Glucose：0.2 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 45 minutes in the above-mentioned copper solution of be adjusted to pH3.0 35 DEG C, make copper colloid Catalyst liquid.

Mantoquita:Deflocculant=1:2, mantoquita:Carbohydrate=1:4, mantoquita:Reducing agent=1:2

(13) embodiment 13

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper methane sulfonate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Xylitol：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Instill reductant solution to stir 45 minutes in the above-mentioned copper solution of be adjusted to pH5.0 35 DEG C, make copper colloid Catalyst liquid.

(14) embodiment 14

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper citrate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Sorbierite：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

(15) embodiment 15

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Formic acid：0.2 mole/L

Xylitol：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

(16) embodiment 16

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Lactic acid：0.2 mole/L

Xylitol：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

(17) embodiment 17

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Nitrilotriacetic acid：0.2 mole/L

Sorbierite：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

(18) embodiment 18

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Sorbierite：0.3 mole/L

[reductant solution]

Dimethylamine borane：0.02 mole/L

Ascorbic acid：0.18 mole/L

(19) embodiment 19

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Mannitol：0.3 mole/L

[reductant solution]

Dimethylamine borane：0.02 mole/L

Ascorbic acid：0.18 mole/L

(20) embodiment 20

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

EDTA：0.2 mole/L

Xylitol：0.3 mole/L

[reductant solution]

Dimethylamine borane：0.02 mole/L

Ascorbic acid：0.18 mole/L

Instill reductant solution to stir 45 minutes in the above-mentioned copper solution of be adjusted to pH9.0 25 DEG C, make copper colloid Catalyst liquid.

The average grain diameter of the copper colloidal particle generating is about 30nm.

(21) comparative example 1

Based on above-described embodiment 1, but in copper colloid catalyst liquid, do not contain the sky of deflocculant and carbohydrate White example.

That is, absorption promotes, catalyst gives, treatment conditions of electroless copper each operation and containing adsorption enhancer The composition of liquid and chemical bronze plating liquid is same as Example 1, and the preparation condition of copper colloid catalyst liquid is as follows.

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Mantoquita:Deflocculant=1:0, mantoquita:Reducing agent=1:2

Generate copper colloidal particle, but condense, precipitate.

(22) comparative example 2

Based on above-described embodiment 1, the regulation containing deflocculant and with the present invention in copper colloid catalyst liquid The example of different carbohydrate (starch).

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

Starch：0.3 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Mantoquita:Deflocculant=1:2, mantoquita:Carbohydrate (starch)=1:3, mantoquita:Reducing agent=1:2

The average grain diameter of the copper colloidal particle generating is about 200nm.

(23) comparative example 3

Based on above-described embodiment 1, omit the example that absorption promotes operation.

That is, sample substrate is not implemented with absorption promotion to process, direct impregnation is carried out in catalyst liquid (b) of embodiment 1 Catalyst gives, and then carries out electroless copper using the plating solution (c) of embodiment 1.Catalyst gives, the place of electroless copper each operation Each preparation condition of manage bar part and copper colloid catalyst liquid and chemical bronze plating liquid is same as Example 1.

(24) benchmark example

Carry out according to above-mentioned first invention, be therefore based on above-described embodiment 1, contain colloid in catalyst liquid steady Determine agent but the example of non-carbohydrate containing.

The preparation of (b) copper colloid catalyst liquid

[copper solution]

Copper sulphate is (with Cu²⁺Meter)：0.1 mole/L

Citric acid：0.2 mole/L

[reductant solution]

Sodium borohydride：0.02 mole/L

Hypophosphorous acid：0.18 mole/L

Mantoquita:Deflocculant=1:2, mantoquita:Carbohydrate (starch)=1:0, mantoquita:Reducing agent=1:2

《The ageing stability test example of catalyst liquid》

Accordingly, for each copper colloid catalyst liquid building bath in above-described embodiment 1～20, comparative example 1～3 and benchmark example, Evaluate the quality of colloidal stability according to following standard.

◎：Do not occurred through more than 2 months after building bath to precipitate or decompose yet.

○：There is precipitation within building bath latter more than 1 month 2 months or decompose.

△：Build to bathe and precipitation occurs in latter 1 month or decomposes.

×：Do not generate colloidal particle, or build precipitation or decomposition at once after bath.

《The ocular estimate test example of the copper envelope being separated out by electroless copper》

Then, for each copper colloid catalyst liquid building bath in above-described embodiment 1～20, comparative example 1～3 and benchmark example, According to following standard visual valuation using the quality building gained plated copper film outward appearance in the case of the catalyst liquid at bath initial stage.

○：The uniform no speckle of plated copper film.

△：Speckle in plated copper film or local does not separate out (plated film defect).

×：Copper envelope does not separate out.

Should illustrate, " speckle " of separating out envelope represents there is envelope compactness or flatness etc. and portions different around Point." speckle " of envelope is the viewpoints different from the uniformity of envelope.

《Ageing stability to copper colloid catalyst liquid and the result of the test by film outward appearance》

《The ageing stability of catalyst liquid and the overall merit of plated film outward appearance》

Do not contain in the comparative example 1 of deflocculant and carbohydrate in copper colloid catalyst liquid, catalyst liquid through when Stability is poor, even and if implementing chemical plating to non-conductive substrate after contacting with catalyst liquid and also do not separate out copper envelope.

On the other hand, in the benchmark example that catalyst liquid contains deflocculant and non-carbohydrate containing, show and urge There is not the good ageing stability precipitating in agent liquid, the outward appearance of copper envelope is good through 1 month after building bath yet.

But, in the catalyst liquid that deflocculant and carbohydrate coexist, using with spy given to this invention Determine the different starch of carbohydrate as the comparative example 2 of this carbohydrate, ageing stability decline makes catalyst liquid institute The copper particle generating is not fine, and plated film defect in the copper envelope of formation, is produced problem by film outward appearance.

Not carrying out absorption in non-conductive substrate promotes process directly to carry out catalyst imparting, then implements electroless copper In comparative example 3, the ageing stability of catalyst liquid is identical with embodiment, but plated film defect in the copper envelope separating out, therefore may be used To judge that not carrying out absorption due to catalyst before giving promotes pretreatment, so catalyst activity is not enough, copper colloidal particle pair The absorption of substrate is poor compared with embodiment.

On the other hand, after carrying out absorption promotion pretreatment, carry out catalyst imparting process, then implement electroless copper In embodiment 1～20, the ageing stability of catalyst liquid is all excellent, the copper envelope that chemical plating is separated out substantially no speckle or plated film Defect, presents excellent outward appearance.

Said reference example is understood with comparative example 1 contrast, the good copper quilt of the outward appearance in order to obtain no speckle or plated film defect Film, not only must contain mantoquita and reducing agent it is necessary to contain deflocculant in catalyst liquid.

On the other hand, above-described embodiment 1～20 is understood with the contrast of this benchmark example, in order to obtain the copper quilt of excellent appearance Film, needs the specific carbohydrate making deflocculant and the present invention to coexist in catalyst liquid.If being especially conceived to catalysis The ageing stability of agent liquid, although then benchmark example shows that building the bath estimation of stability of latter more than 1 month is zero, embodiment 1 ～20 each catalyst liquid shows builds the stability more than 2 months after bath, shows for this ageing stability, and embodiment 1～ 20 each catalyst liquid phase has an advantage for benchmark example, and have can make catalyst liquid maintenance more simpler than benchmark example Change the advantage such that it is able to mitigate the processing cost of electroless copper.

In addition, comparative example 2 and the embodiment 1 of the starch different from specific carbohydrate given to this invention will be used ～20 contrasts understand, even if in the case that deflocculant is coexisted in catalyst liquid with carbohydrate, if not selecting this The specific carbohydrate of invention defined, then will not improve the ageing stability of catalyst liquid, cannot smoothly be formed on the contrary Fine copper colloidal particle, result can be damaged by film outward appearance, therefore can determine whether to select specific carbohydrate to raising catalyst The importance of the ageing stability of liquid.

Then, embodiment 1～20 is discussed in detail.

The relative evaluation of explanation and other embodiment based on embodiment 1.First, embodiment 1 uses and contains cation Type surfactant is that the adsorption enhancer of the quaternary ammonium salt of diallylamine polymers pre-processes to non-conductive substrate, uses With copper sulphate as mantoquita, sodium borohydride as reducing agent, citric acid as deflocculant, xylitol be urging of specific carbohydrate After agent liquid carries out catalyst imparting, carry out the example of electroless copper, the ageing stability of catalyst liquid is good, build after bath through 2 Do not occur within individual month to precipitate or decompose, in addition, the copper envelope of chemical plating gained does not occur separating out speckle or plated film defect, present yet Excellent outward appearance.

Embodiment 2 is the example of the content that carbohydrate is greatly decreased with respect to embodiment 1, otherwise embodiment 3 is significantly Increase the example of the content of carbohydrate, the ageing stability of catalyst liquid is good similarly to Example 1, and gained copper envelope presents Go out excellent outward appearance.

Carbohydrate be changed to sorbierite (sugar alcohol) embodiment 4, be equally changed to mannitol (sugar alcohol) embodiment 5, It is changed to the embodiment 6 of glucolactone (monose analog derivative), be changed to the embodiment 7 of glucose (monosaccharide), be changed to malt The embodiment 8 of sugared (disaccharides), the embodiment 11 being changed to sorbierite and xylitol (sugar alcohol to each other be used in combination), mannitol and Portugal In the embodiment 12 of grape sugar (sugar alcohol with monosaccharide be used in combination), all show high ageing stability and excellent similarly to Example 1 By film outward appearance.

Based on the catalyst liquid of the embodiment 1 containing xylitol, add PVP (mean molecule quantity 4 in catalyst liquid Ten thousand) as in the embodiment 9 of water-soluble polymer, the evaluation of the ageing stability of catalyst liquid and plated film outward appearance and embodiment 1 Identical.

Based on the catalyst liquid of the embodiment 4 containing sorbierite, add PEG (mean molecule quantity 1 in catalyst liquid Ten thousand) as in the embodiment 10 of water-soluble polymer, the evaluation of the ageing stability of catalyst liquid and plated film outward appearance and embodiment 4 Identical.

Even if in addition, based on embodiment 1,4 or 5, changing soluble copper salt, deflocculant, reducing agent (with reference to real Apply example 13～19), also show with each basis high ageing stability of embodiment identical and excellent by film outward appearance.

It is set as the embodiment 1 of pH4.0 with respect to catalyst liquid, in the embodiment 20 of the pH9 being set as alkalescent side, Equally show high ageing stability and excellent by film outward appearance.

Embodiment 4 and embodiment 11 are after catalyst imparting is processed and carry out pickling and carry out electroless copper again processing it , especially the apparent difference of envelope, even if implement heat treatment is by between face and substrate compared with other embodiment in example Do not change, can confirm that high adhesion yet.

Claims

1. a kind of electroless copper copper colloid catalyst liquid, is to carry out for contacting with the non-conductive substrate implementing electroless copper The copper colloid catalyst liquid that catalyst gives is it is characterised in that contain：

(A) soluble copper salt；

(B) reducing agent；

(C) it is selected from monocarboxylic acid class, hydroxycarboxylic acid, the deflocculant in aminocarboxylic acids and polybasic carboxylic acid class extremely Few one kind；And

(D) it is selected from glucose, fructose, lactose, maltol, isomaltoketose, wood sugar, sorbierite, xylitol, mannitol, malt Carbon hydrate in sugar alcohol, antierythrite, reduction starch syrup, lactitol, reduction isomaltoketose and glucolactone At least one of thing.

2. electroless copper according to claim 1 with copper colloid catalyst liquid it is characterised in that described soluble-salt (A) Content mol ratio with described deflocculant (C) is A:C=1:0.03～1:35.

3. electroless copper according to claim 1 and 2 with copper colloid catalyst liquid it is characterised in that described electroless copper Also contained selected from polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide with copper colloid catalyst liquid At least one of the synthesis class water-soluble polymer in amine and polyethyleneimine.

4. electroless copper according to any one of claim 1 to 3 with copper colloid catalyst liquid it is characterised in that described Reducing agent (B) is selected from hydroboron, amine borine class, hypophosphorous acid class, aldehydes, Vitamin C acids, hydrazine, polyatomic phenol, many At least one in first aphthols, phenolsulfonic acid class, naphtholsulfonic acid class and sulfinic acid class.

5. electroless copper according to any one of claim 1 to 4 with copper colloid catalyst liquid it is characterised in that described Described monocarboxylic acid class in deflocculant (C) be selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, capric acid, At least one in laurate, myristic acid, palmitic acid, stearic acid and their salt；

Described hydroxycarboxylic acid be selected from citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic, lactic acid, three Hydroxybutyric acid, ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine, citramalic acid and they Salt at least one；

Described aminocarboxylic acids is selected from hydroxyethylethylene diamine tri-acetic acid, diethylene-triamine pentaacetic acid, trien six Acetic acid, ethylenediamine tetra-acetic acid, ethylenediamine tetrapropionic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, imido Base dipropionic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- diaminourea -2- hydroxy propane tetraacethyl, glycoletherdiaminotetraacetic acid, isophthalic Ethylenediamine tetraacetic acid (EDTA), 1,2- cyclohexanediamine-N, N, N ', N '-tetraacethyl, diaminopropionic acid, glutamic acid, two carboxymethyl glutamic acid, bird Propylhomoserin, cysteine, N, in N- bis- (2- ethoxy) glutamic acid, (S, S)-ethylenediamine butanedioic acid and their salt at least A kind of；

Described polybasic carboxylic acid class is selected from butanedioic acid, glutaric acid, malonic acid, adipic acid, ethanedioic acid, maleic acid, citraconic acid, clothing health At least one in acid, mesaconic acid and their salt.

6. a kind of electroless copper plating method is it is characterised in that include：

A () absorption promotes operation (pretreatment process), non-conductive substrate is immersed in the liquid containing adsorption enhancer, institute State adsorption enhancer be selected from nonionic surface active agent, cationic surface active agent, anionic surfactant and At least one in amphoteric surfactant；

B () catalyst gives operation, non-conductive substrate is immersed in the copper colloid any one of claim 1 to 5 and urges In agent liquid, make copper colloid particle absorption on the surface of the substrate；And

7. electroless copper plating method according to claim 6 is it is characterised in that the adsorption enhancer of described operation (a) is sun Ionic surfactant and/or amphoteric surfactant.

8. adopt the electroless copper plating method described in claim 6 or 7 to form the non-conductive substrate of copper envelope.